Optimizing Eg Orbital Occupancy of Transition Metal Sulfides by Building Internal Electric Fields to Adjust the Adsorption of Oxygenated Intermediates for Li‐O2 Batteries

Abstract Li‐O 2 batteries are acknowledged as one of the most promising energy systems due to their high energy density approaching that of gasoline, but the poor battery efficiency and unstable cycling performance still hinder their practical application. In this work, hierarchical NiS 2 ‐MoS 2 heterostructured nanorods are designed and successfully synthesized, and it is found that heterostructure interfaces with internal electric fields between NiS 2 and MoS 2 optimized e g orbital occupancy, effectively adjusting the adsorption of oxygenated intermediates to accelerate reaction kinetics of oxygen evolution reaction and oxygen reduction reaction. Structure characterizations coupled with density functional theory calculations reveal that highly electronegative Mo atoms on NiS 2 ‐MoS 2 catalyst can capture more e g electrons from Ni atoms, and induce lower e g occupancy enabling moderate adsorption strength toward oxygenated intermediates. It is evident that hierarchical NiS 2 ‐MoS 2 nanostructure with fancy built‐in electric fields significantly boosted formation and decomposition of Li 2 O 2 during cycling, which contributed to large specific capacities of 16528/16471 mAh g −1 with 99.65% coulombic efficiency and excellent cycling stability of 450 cycles at 1000 mA g −1 . This innovative heterostructure construction provides a reliable strategy to rationally design transition metal sulfides by optimizing e g orbital occupancy and modulating adsorption toward oxygenated intermediates for efficient rechargeable Li‐O 2 batteries.